CN107502275A - A kind of fire-retardant antistripping adhesive for polyurethane - Google Patents

A kind of fire-retardant antistripping adhesive for polyurethane Download PDF

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Publication number
CN107502275A
CN107502275A CN201710888787.3A CN201710888787A CN107502275A CN 107502275 A CN107502275 A CN 107502275A CN 201710888787 A CN201710888787 A CN 201710888787A CN 107502275 A CN107502275 A CN 107502275A
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parts
retardant
fire
adhesive
antistripping
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朱立芳
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ANHUI BIG PINE RESIN Co Ltd
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ANHUI BIG PINE RESIN Co Ltd
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Priority to CN201710888787.3A priority Critical patent/CN107502275A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K2003/387—Borates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/00—Polymer mixtures characterised by other features
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a kind of fire-retardant antistripping adhesive for polyurethane, its raw material includes：1,5 naphthalene diisocyanates, XDI, PTMG, polyadipate castor oil ester polyalcohol, 3,3 ' dichloro-4,4s, 4 ' diaminodiphenyl-methanes, hydroxy silicon oil, glycerine, filler, modifying agent, epoxidized soybean oil, epoxyoleic acid, castor oil, fibroin albumen, fire retardant, cystine dimethyl；The fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite.Fire-retardant antistripping adhesive for polyurethane proposed by the present invention, it has excellent anti-flammability, heat resistance and water resistance, and curing rate is fast, high with the adhesion strength of base material, antistripping.

Description

A kind of fire-retardant antistripping adhesive for polyurethane
Technical field
The present invention relates to adhesive technical field, more particularly to a kind of fire-retardant antistripping adhesive for polyurethane.
Background technology
Adhesive refers to act on cohesion etc. by sticking for interface, can connect two or more product or material Natural or synthesis, the organic or inorganic a kind of material being connected together, can according to chemical composition be divided into epoxide-resin glue Glutinous agent, adhesive for polyurethane, polyvinyl acetate adhesive etc..
Adhesive for polyurethane refers to the adhesive containing carbamate groups or NCO, its point in strand Containing the isocyanates and carbamate groups that polarized is very strong, chemical activity is very high in son, with foamed plastics, timber, skin The porous materials such as leather, fabric, paper, ceramics, and any surface finish such as metal, glass, rubber, plastics material suffer from it is excellent Chemical adhesion, and toughness, controllability are good, and resistance to low temperature is excellent, has been widely used in civilian, physical culture, boat at present My god, the field such as military affairs, turn into one of indispensable important materials.But because anti-flammability is not good enough, deposited with its manufactured adhesive The anti-flammability and not good enough stripper-resistance the defects of, its application receives a certain degree of limitation.
The content of the invention
Based on technical problem existing for background technology, the present invention proposes a kind of fire-retardant antistripping adhesive for polyurethane, its With excellent anti-flammability, heat resistance and water resistance, and curing rate is fast, high with the adhesion strength of base material, antistripping.
A kind of fire-retardant antistripping adhesive for polyurethane proposed by the present invention, its raw material include by weight：1,5- naphthalenes two are different Cyanate 10-35 parts, XDI 2-13 parts, PTMG 15-30 parts, polyadipate castor-oil plant Grease polyalcohol 5-25 parts, 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methane 0.1-0.5 parts, hydroxy silicon oil 0.2-1.5 parts, Glycerine 2-5 parts, filler 2-8 parts, modifying agent 1-3 parts, epoxidized soybean oil 2-4.5 parts, epoxyoleic acid 2-10 parts, castor oil 0.5- 3 parts, fibroin albumen 1-4 parts, fire retardant 3-12 parts, cystine dimethyl 0.2-1.3 parts；
Wherein, the fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite.
Preferably, the filler is graphene oxide, nano-calcium carbonate, titanium dioxide, CNT, chlorite, barite In one or more kinds of mixtures.
Preferably, the filler is by the graphene oxide of 2-10 parts by weight, the nano-calcium carbonate of 1-5 parts by weight, 0.5-3 weights Measure the titanium dioxide of part, the CNT of 5-15 parts by weight, the chlorite of 0.5-3.8 parts by weight, 2-10 parts by weight barite with The beta-schardinger dextrin of 0.5-2 parts by weight is added in ethanol and is uniformly mixing to obtain.
Preferably, the modifying agent is prepared according to following technique：Phenol and paraformaldehyde are added in toluene, stirring Be warming up to 48-55 DEG C after uniformly, add the mixture of allylamine and toluene, after stirring back flow reaction 3-8h, reaction terminate Through extracting, being filtrated to get material A；Material A, styrene, butyl acrylate and benzoyl peroxide are added in toluene, in nitrogen Protection under react 30-50min, the temperature of reaction is 65-75 DEG C, adds the mixing of maleic anhydride, benzoyl peroxide, acetone Thing, reacts 50-80min at 70-85 DEG C, reaction terminate after through precipitating, filtering, being dried to obtain material B；By material B, three second Amine, silane resin acceptor kh-550 are added in dichloromethane, are stirred under nitrogen protection, react at room temperature 5-15h, and reaction terminates By precipitating, filter, wash, be dried to obtain the modifying agent.
Preferably, phenol, paraformaldehyde, the weight ratio of allylamine are 3.5-4.5：2.5-4：3-5.
Preferably, material A, styrene, butyl acrylate, the weight ratio of maleic anhydride are 1-5：2-10：3-7：1-5.
Preferably, material B, the weight ratio of silane resin acceptor kh-550 are 2-5：0.2-1.
Preferably, in fire retardant, thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, the weight of cobalt zeolite Than for 2-10：1-4：2-5：3-10.
Preferably, in its raw material, the solvent of 30-50 parts by weight is included.
Preferably, the solvent is tetrahydrofuran, acetone, butanone, dimethyl sulfoxide (DMSO), DMF, N, N- One or more kinds of mixtures in dimethyl acetamide, ether.
Fire-retardant antistripping adhesive for polyurethane of the present invention, in its raw material, with 1,5- naphthalene diisocyanates, the methylene of benzene two Group diisocyanate, PTMG, polyadipate castor oil ester polyalcohol are raw material, while add hydroxy silicon oil And glycerine, make gained adhesive for polyurethane that there is excellent heat resistance and water resistance, significantly improve the adhesion strength of adhesive； Epoxidized soybean oil, the epoxyoleic acid of addition for during, can occur ring-opening reaction, obtain epoxy soybean in polyurethane Oil-oleic acid polyalcohol, the heat-resisting of adhesive, stretching and cutting performance are significantly improved in system, while significantly improved poly- The peel strength of urethane adhesive；The fibroin albumen of addition can significantly improve the intensity of adhesive for polyurethane；In fire retardant, with sulphur It is raw material for cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite, there is excellent synergisticing performance, significantly carry The high heat resistance of adhesive, mechanical property and anti-flammability；In the preparation process of preferred embodiment modifying agent, first with phenol, more Polyformaldehyde and allylamine are raw material, are reacted phenol, paraformaldehyde and allylamine, have obtained the oxazine of phenylpropyl alcohol containing pi-allyl Material A, material A and styrene, butyl acrylate, maleic anhydride are reacted afterwards, so as to by material A, styrene, acrylic acid Butyl ester, maleic anhydride are combined as a whole, and have obtained material B, silane coupled after material B is mixed with silane resin acceptor kh-550 Amino in agent KH-550 is reacted with material B, so as to by the material A of the oxazine of phenylpropyl alcohol containing pi-allyl, styrene, acrylic acid Butyl ester, maleic anhydride, silane resin acceptor kh-550 are combined as a whole, and have obtained modifying agent, are added into system, on the one hand have There is coupling agent, significantly improve the compatibility of adhesive, assign adhesive excellent stripper-resistance, on the other hand, show Writing improves the heat resistance and water resistance of adhesive.
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of fire-retardant antistripping adhesive for polyurethane proposed by the present invention, its raw material include by weight：1,5- naphthalenes two are different 35 parts of cyanate, 2 parts of XDI, 30 parts of PTMG, polyadipate castor oil ester are polynary 5 parts of alcohol, 3,3 '-two chloro- 0.5 part of 4,4 '-diaminodiphenyl-methanes, 0.2 part of hydroxy silicon oil, 5 parts of glycerine, 2 parts of filler, modification 3 parts of agent, 2 parts of epoxidized soybean oil, 10 parts of epoxyoleic acid, 0.5 part of castor oil, 4 parts of fibroin albumen, 3 parts of fire retardant, cystine two 1.3 parts of methyl esters；
Wherein, the fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite.
Embodiment 2
A kind of fire-retardant antistripping adhesive for polyurethane proposed by the present invention, its raw material include by weight：1,5- naphthalenes two are different 10 parts of cyanate, 13 parts of XDI, 15 parts of PTMG, polyadipate castor oil ester are polynary 25 parts of alcohol, 3,3 '-two chloro- 0.1 part of 4,4 '-diaminodiphenyl-methanes, 1.5 parts of hydroxy silicon oil, 2 parts of glycerine, 8 parts of filler, change 1 part of agent of property, 4.5 parts of epoxidized soybean oil, 2 parts of epoxyoleic acid, 3 parts of castor oil, 1 part of fibroin albumen, 12 parts of fire retardant, cystine 0.2 part of dimethyl ester；
Wherein, the fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite.
Embodiment 3
A kind of fire-retardant antistripping adhesive for polyurethane proposed by the present invention, its raw material include by weight：1,5- naphthalenes two are different 33 parts of cyanate, 7 parts of XDI, 26 parts of PTMG, polyadipate castor oil ester are polynary 9 parts of alcohol, 3,3 '-two chloro- 0.42 part of 4,4 '-diaminodiphenyl-methanes, 0.4 part of hydroxy silicon oil, 4.3 parts of glycerine, graphite oxide It is 4 parts of alkene, 2.7 parts of modifying agent, 2.6 parts of epoxidized soybean oil, 9 parts of epoxyoleic acid, 1 part of castor oil, 3.2 parts of fibroin albumen, fire-retardant 5 parts of agent, 1 part of cystine dimethyl, 38 parts of tetrahydrofuran；
Wherein, the fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite, And the weight ratio of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite is 10：1：5：3；
The modifying agent is prepared according to following technique：Phenol and paraformaldehyde are added in toluene, after stirring 55 DEG C are warming up to, adds the mixture of allylamine and toluene, wherein, phenol, paraformaldehyde, the weight ratio of allylamine are 4.5： 2.5：5, back flow reaction 3h after stirring, reaction terminate through extracting, being filtrated to get material A；By material A, styrene, acrylic acid Butyl ester and benzoyl peroxide are added in toluene, 30min are reacted under the protection of nitrogen, the temperature of reaction is 75 DEG C, adds horse Carry out the mixture of acid anhydrides, benzoyl peroxide, acetone, wherein, material A, styrene, butyl acrylate, the weight of maleic anhydride Than for 1：10：3：5, react 80min at 70 DEG C, reaction terminate after through precipitating, filtering, being dried to obtain material B；By material B, three Ethamine, silane resin acceptor kh-550 are added in dichloromethane, wherein, material B, the weight ratio of silane resin acceptor kh-550 are 2：1, Stir under nitrogen protection, react at room temperature 5h, reaction terminate after through precipitating, filtering, washing, being dried to obtain the modification Agent.
Embodiment 4
A kind of fire-retardant antistripping adhesive for polyurethane proposed by the present invention, its raw material include by weight：1,5- naphthalenes two are different 15 parts of cyanate, 11 parts of XDI, 20 parts of PTMG, polyadipate castor oil ester are polynary 20 parts of alcohol, 3,3 '-two chloro- 0.25 part of 4,4 '-diaminodiphenyl-methanes, 1.3 parts of hydroxy silicon oil, 2.6 parts of glycerine, 7 parts of filler, 1.6 parts of modifying agent, 4 parts of epoxidized soybean oil, 3.2 parts of epoxyoleic acid, 2.7 parts of castor oil, 2 parts of fibroin albumen, 10 parts of fire retardant, 0.4 part of cystine dimethyl, 10 parts of butanone, 12 parts of dimethyl sulfoxide (DMSO), 21 parts of N,N-dimethylformamide；
Wherein, the fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite, And the weight ratio of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite is 2：4：2：10；
The filler by the graphene oxide of 10 parts by weight, the nano-calcium carbonate of 5 parts by weight, 0.5 parts by weight titanium dioxide, The CNT of 15 parts by weight, the chlorite of 0.5 parts by weight, the barite of 10 parts by weight and the beta-schardinger dextrin of 0.5 parts by weight add Enter in ethanol and be uniformly mixing to obtain；
The modifying agent is prepared according to following technique：Phenol and paraformaldehyde are added in toluene, after stirring 48 DEG C are warming up to, adds the mixture of allylamine and toluene, wherein, phenol, paraformaldehyde, the weight ratio of allylamine are 3.5：4： 3, back flow reaction 8h after stirring, reaction terminate through extracting, being filtrated to get material A；By material A, styrene, butyl acrylate Added with benzoyl peroxide in toluene, 50min is reacted under the protection of nitrogen, the temperature of reaction is 65 DEG C, adds maleic acid Acid anhydride, benzoyl peroxide, the mixture of acetone, wherein, material A, styrene, butyl acrylate, the weight ratio of maleic anhydride are 5：2：7：1, react 50min at 85 DEG C, reaction terminate after through precipitating, filtering, being dried to obtain material B；By material B, triethylamine, Silane resin acceptor kh-550 is added in dichloromethane, wherein, material B, the weight ratio of silane resin acceptor kh-550 are 5：0.2, Stirred under nitrogen atmosphere is uniform, reacts at room temperature 15h, reaction terminate after through precipitating, filtering, washing, being dried to obtain the modifying agent.
Embodiment 5
A kind of fire-retardant antistripping adhesive for polyurethane proposed by the present invention, its raw material include by weight：1,5- naphthalenes two are different 32 parts of cyanate, 10 parts of XDI, 20 parts of PTMG, polyadipate castor oil ester are polynary 17 parts of alcohol, 3,3 '-two chloro- 0.3 part of 4,4 '-diaminodiphenyl-methanes, 1 part of hydroxy silicon oil, 4 parts of glycerine, 6 parts of filler, modification 1.8 parts of agent, 4 parts of epoxidized soybean oil, 7.6 parts of epoxyoleic acid, 2 parts of castor oil, 3 parts of fibroin albumen, 10 parts of fire retardant, cystine 1 part of dimethyl ester, 40 parts of solvent；
Wherein, the fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite, And the weight ratio of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite is 7：3：4：9；
The filler by the graphene oxide of 2 parts by weight, the nano-calcium carbonate of 1 parts by weight, 3 parts by weight titanium dioxide, 5 weights The beta-schardinger dextrin for measuring the CNT of part, the chlorite of 3.8 parts by weight, the barite of 2 parts by weight and 2 parts by weight is added in ethanol It is uniformly mixing to obtain；
The modifying agent is prepared according to following technique：Phenol and paraformaldehyde are added in toluene, after stirring 50 DEG C are warming up to, adds the mixture of allylamine and toluene, wherein, phenol, paraformaldehyde, the weight ratio of allylamine are 4：3：4, Back flow reaction 7h after stirring, reaction terminate through extracting, being filtrated to get material A；By material A, styrene, butyl acrylate and Benzoyl peroxide is added in toluene, and 40min is reacted under the protection of nitrogen, and the temperature of reaction is 70 DEG C, addition maleic anhydride, The mixture of benzoyl peroxide, acetone, wherein, material A, styrene, butyl acrylate, the weight ratio of maleic anhydride are 3：8： 6：4, react 75min at 78 DEG C, reaction terminate after through precipitating, filtering, being dried to obtain material B；By material B, triethylamine, silane Coupling agent KH-550 is added in dichloromethane, wherein, material B, the weight ratio of silane resin acceptor kh-550 are 3：0.7, in nitrogen Stirred under protection, react at room temperature 12h, reaction terminate after through precipitating, filtering, washing, being dried to obtain the modifying agent；
The solvent is tetrahydrofuran, acetone, butanone, dimethyl sulfoxide (DMSO), N,N-dimethylformamide, N, N- dimethyl second The mixture of acid amides, ether, and tetrahydrofuran, acetone, butanone, dimethyl sulfoxide (DMSO), DMF, N, N- dimethyl Acetamide, the weight ratio of ether are 3：4：2：3：4：5：1.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.

Claims (10)

1. a kind of fire-retardant antistripping adhesive for polyurethane, it is characterised in that its raw material includes by weight：The isocyanic acid of 1,5- naphthalenes two Ester 10-35 parts, XDI 2-13 parts, PTMG 15-30 parts, polyadipate castor oil ester Polyalcohol 5-25 parts, 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methane 0.1-0.5 parts, hydroxy silicon oil 0.2-1.5 parts, glycerine 2-5 parts, filler 2-8 parts, modifying agent 1-3 parts, epoxidized soybean oil 2-4.5 parts, epoxyoleic acid 2-10 parts, castor oil 0.5-3 parts, Fibroin albumen 1-4 parts, fire retardant 3-12 parts, cystine dimethyl 0.2-1.3 parts；
Wherein, the fire retardant is made up of thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, cobalt zeolite.
2. fire-retardant antistripping adhesive for polyurethane according to claim 1, it is characterised in that the filler is graphite oxide One or more kinds of mixtures in alkene, nano-calcium carbonate, titanium dioxide, CNT, chlorite, barite.
3. fire-retardant antistripping adhesive for polyurethane according to claim 1 or claim 2, it is characterised in that the filler is by 2-10 weights Measure the graphene oxide of part, the nano-calcium carbonate of 1-5 parts by weight, the titanium dioxide of 0.5-3 parts by weight, the carbon nanometer of 5-15 parts by weight Pipe, the barite of the chlorite of 0.5-3.8 parts by weight, 2-10 parts by weight and the beta-schardinger dextrin of 0.5-2 parts by weight are added in ethanol It is uniformly mixing to obtain.
4. the fire-retardant antistripping adhesive for polyurethane according to any one of claim 1-3, it is characterised in that the modifying agent Prepared according to following technique：Phenol and paraformaldehyde are added in toluene, 48-55 DEG C is warming up to after stirring, is added The mixture of allylamine and toluene, back flow reaction 3-8h after stirring, reaction terminate through extracting, being filtrated to get material A；By thing Expect that A, styrene, butyl acrylate and benzoyl peroxide are added in toluene, 30-50min is reacted under the protection of nitrogen, react Temperature be 65-75 DEG C, add maleic anhydride, benzoyl peroxide, the mixture of acetone, react 50- at 70-85 DEG C 80min, reaction terminate after through precipitating, filtering, being dried to obtain material B；Material B, triethylamine, silane resin acceptor kh-550 are added In dichloromethane, stir under nitrogen protection, react at room temperature 5-15h, reaction terminate after through precipitating, filtering, washing, dry Obtain the modifying agent.
5. fire-retardant antistripping adhesive for polyurethane according to claim 4, it is characterised in that phenol, paraformaldehyde, allylamine Weight ratio be 3.5-4.5：2.5-4：3-5.
6. according to the fire-retardant antistripping adhesive for polyurethane of claim 5 or 6, it is characterised in that material A, styrene, propylene Acid butyl ester, the weight ratio of maleic anhydride are 1-5：2-10：3-7：1-5.
7. the fire-retardant antistripping adhesive for polyurethane according to any one of claim 4-6, it is characterised in that material B, silane Coupling agent KH-550 weight ratio is 2-5：0.2-1.
8. the fire-retardant antistripping adhesive for polyurethane according to any one of claim 1-7, it is characterised in that in fire retardant, Thio cage-like pentaerythritol phosphate, nano boric acid lanthanum, hydrotalcite, the weight ratio of cobalt zeolite are 2-10：1-4：2-5：3-10.
9. the fire-retardant antistripping adhesive for polyurethane according to any one of claim 1-8, it is characterised in that in its raw material, Also include the solvent of 30-50 parts by weight.
10. fire-retardant antistripping adhesive for polyurethane according to claim 9, it is characterised in that the solvent be tetrahydrofuran, It is one or more kinds of in acetone, butanone, dimethyl sulfoxide (DMSO), N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, ether Mixture.
CN201710888787.3A 2017-09-27 2017-09-27 A kind of fire-retardant antistripping adhesive for polyurethane Withdrawn CN107502275A (en)

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CN116623468A (en) * 2023-06-28 2023-08-22 杭州锦宏装饰纸有限公司 Heat-resistant flame-retardant decorative paper and preparation method thereof

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN109554151A (en) * 2018-10-23 2019-04-02 厦门韦尔通科技有限公司 A kind of adhesive and preparation method thereof suitable for electronic device
WO2023103480A1 (en) * 2021-12-07 2023-06-15 襄阳三沃航天薄膜材料有限公司 High-performance polyurethane pressure-sensitive adhesive, preparation method therefor, and application thereof
CN114350299A (en) * 2022-01-17 2022-04-15 万华化学集团股份有限公司 Thiol protein fiber modified PUR hot melt adhesive and preparation method thereof
CN114350299B (en) * 2022-01-17 2023-05-26 万华化学集团股份有限公司 Thiol protein fiber modified PUR hot melt adhesive and preparation method thereof
CN116554673A (en) * 2023-05-16 2023-08-08 广东技塑新材料股份有限公司 Degradable TPU (thermoplastic polyurethane) for shoe material and preparation method thereof
CN116554673B (en) * 2023-05-16 2023-12-19 广东技塑新材料股份有限公司 Degradable TPU (thermoplastic polyurethane) for shoe material and preparation method thereof
CN116623468A (en) * 2023-06-28 2023-08-22 杭州锦宏装饰纸有限公司 Heat-resistant flame-retardant decorative paper and preparation method thereof

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